P R E P A R A T I O N OF IRON POWDER BY THE T H E R M A L D E C O M P O S I T I O N

OF IRON P E N T A C A R B O N Y L

V. G. S y r k i n

MOSCOW
Translated from Poroshkovaya Metallurgiya, No. 3(21),
pp. 75-84, May-June, i964
Original article submitted January 27, i963

The extensive deveIopment of radio electronics has set before Soviet industry the task of producing fine
ferromagnetic carbonyl iron powders for the manufacture of sintered magnetic cores having high electromagnetic
properties in a wide frequency range.

The quality of earbonyl iron powder intended for the manufacture of cores operating at frequencies above 50
Mcps is evaluated according to Technical Specification STU-12 N 10-210-62, on the basis of the electromagnetic
parameters of type STsG-2 cylindrical cores. The industrially produced carbonyl iron powder with the bulk of parti-
cles 0.5,4 g in size is assessed at a frequency of 50 Mcps by its Q-factor ('goodness factor") (Qrel. = 0.90-0.95) and
effective magnetic permeability (/1 ef. = 1.40-1.45).

Smaller particle size of iron powder improves the electromagnetic properties of electronic cores made from
such powder [1, 2]. For example, by using iron powder with particles mainly 0.5-2.0 g in size, it is possible to attain
(with appropriate powder insulation), at a frequency of 50 Mcps, values of Qrel. = 1.12 and /lef" = 1.62,with adequate
temperature stability of the sintered material [8].

However, with the present, direct method of production of carbonyl iron powder, based on the vapor-phase
decomposition of iron pentacarbonyl, Fe (CO)5, in the presence of ammonia, it is not possible to produce such powder.
The fraction with the predominant particle size of 0.5-2 g can only be obtained from carbonyl iron powder by
separation in a system of cyclones connected in series [3]. It should be noted that, with this process, the basic carbonyl
plant must be supplemented by a complex installation consisting of several series of cyclones, and this in turn involves
increased expenditure of electric power, gas, etc., not to mention the need for additional shop floor space and
operating personnel.

The present paper describes a new method for producing fine iron powders, with particles mainly 0.5-1.0 ~ in
size, directly in the carbonyl process, in which atomized iron pentacarbonyl is fed into the thermal decomposition
apparatus by centrifugal nozzles of tangential or screw types.

Brief Analysis of the V a p o r - P h a s e Decomposition of I r o n P e n t a c a r b o n y _ l _

The existing process is based on the fact that, at a temperature of the order of 300* C, Fe(CO) s vapors
decompose in a free volume according to the reaction

Fe(CO)5=Fe+5CO
with the absorption of 225 kl/mole of heat. The process is performed in the presence of ammonia. The resultant iron
particles are collected as two powder fractions: 1) a fraction with particles 0.8-7.0 ~t in size (in the decomposition
container); 2) a fraction with particles 0.5-5.0 g in size (in the container of the beta-filter apparatus). However,
both these fractions contain individual particles of larger sizes, as well as conglomerated particles.
The above-described carbonyl process operates continuously, and, generally speaking, has up to now satisfied
the present-day engineering requirements in spite of the following disadvantages:
1. Feeding is performed through a nozzle with a calibrated orifice, through which liquid carbonyl passes by
gravity into the vaporizer. This leads to the gradual clogging up of the nozzle and reduction of Fe(CO)5 feed.

232

&lC4
ti 7
Fig. 1. Diagram of installation for production of iron
powder by decomposition of atomized i r o n p e n t a c a r b o n y h
1) container with iron pentacarbonyl; 2) coarse filters;
3) fine filter; 4 ) h e a d with nozzle; 5) decomposition
apparatus; 6 and 8) powder collecting tanks; 7) b e t a -
filter; 9) waste gas rotameter; 10) a m m o n i a cylinder;
11) a m m o n i a rotameter; 12) CO cylinder; 13) nitrogen
cyIinder; 14) CO or nitrogen rotameter; 16, 16, and 17)
pressure reducing valves; 18) discharge from iron penta-
carbonyl container.
section A-A
1 but also to the deposition of secondary-reaction pro-
~ ~-LI/IIIflIIitIA
I
Fig. 2 Centrifugal nozzte of tangential type ( 0 =
diameter, in ram)
Fig. 3. Centrifugal nozzle of screw type (0:
diameter, in ram)
2. Since the carbonyl evaporates in thevaporizer,
it is necessary p e r i o d i c a l l y to stop the process in order
to c l e a n the vaporizer, as otherwise a solid iron de-
posit builds up on the walls and bottom of the latter,
which strongly reduces heat transfer and leads to a
loss of product.
3. It is impossible to produce fine powders with
the bulk of particles 0.8-1.0 // in size. By employing
separation, a very fine fraction m a y be produced in an
amount not e x c e e d i n g 1% of the whole amount of
powder, but this is clearly insufficient.
The formation of iron powder particles takes
p l a c e in the following manner.Liquid iron penta-
carbonyl enters the vaporizer, where it evaporates at
a t e m p e r a t u r e of about 108 ~ C. On reaching the upper
zone of the thermal decomposition apparatus, Fe(CO)s
vapor molecules dissociate under the influence of
temperature (300 ~ C) with the formation of iron atoms
and carbon monoxide molecules. Groups of iron atoms
join up together and form nuclei of (x-iron crystals
(particles). In the middle and lower zones of the
apparatus, these nuclei grow further and form carbonyl
iron particles.
However, the p a r t i c l e formation process invoNes
also molecules of iron carbides and nitrides, which are
formed in the decomposition zone. Their existence is
due to secondary reactions, taking place during the
decomposition of iron pentacarbonyl in the presence
of a m m o n i a . The growth of an iron carbonyl p a r t i c l e
is due not only to the building up of a - i r o n atoms,
ducts on the primary layers [4]. As a result of such
intermittent growth, the particle acquires the so-
called onion structure, consisting of layers of ~.-iron
and secondary-reaction products.
V. L. Volkov and G. M. Khapov's investigations
have demonstrated that p a r t i c l e size increases all the
t i m e also because of the presence in the thermal de-
composition apparatus of convection currents, which
frequently return particles from the lower and middle
zones to the upper region. Particle growth in fact
ceases only when the weight of the particle becomes
greater than. the lifting force due to the convection
currents. It is precisely because of these convection
currents, which promote particle growrJ~, that the
existing method is unsuitable for the production of
fine powder with the bulk of particies 0.8-1.0y in size.
A. E. Fridenberg and others showed that the
convection currents in the apparatus may be partially
reduced or increased by employing specific t e m p e r a -
ture conditions in each zone. Even this method, how-
ever, fails to yield iron powders with a predominant
p a r t i c l e size of 0.6-1.0 ~.
233
 In order m establish favorableconditions for the
2t~ interruption of particle growth in the size range 0.5-1.0/~,
120
it is necessary- to create Fe(CO)5 dissociation conditions
100 -- ,,~
under which the convection currents are reduced to a
80 /
/ minimum. Investigations have shown that this requirement
50 r [ is satisfied by the new method of decomposing liquid iron
,~0 3
pentacarbonyl without prior vaporization, which will be
zo [
ot 1 [ A examined below [9].
0,5 / t,$ 2 2,53 3,5L~ r
Fig. 4. Effect: of geometrical nozzle characteristic Thermal Decomposition of Atomized Iron
(A) on spray angle of iron pentacarbonyl (o0. Pentacarbonyl
In recent years, great progress has been made both
in the Uo S. S. R. and abroad in the development of mechan-
A ical devices for the generation of sprays of variousliquids.
0,~ The rapid progress in the design of internal combustion
qs engines, including diesels, and the extensive application
o,7
0,6
aA
\ of spraying techniques in agriculture are only a few
examples of the many fields in whtchmicrospraying is

0,4 \ employed. Spraying devices (atomizers) are gradually

being introduced also in the chemical industry for setting
a3 _ \
'.... up automatic continuous processes.
0,2
In this connection, the problem arises whether
o,/ r

O I A atomizing devices could not be used in the carbonyl

0,5/ t5 2 L53 3,5 4 ~,5 5 gs 6 process for the preparation of fine powders, particularly
Fig. 5. Effect of geometrical nozzle characteristic those employed in electronics, since the method of feeding
(A) on coefficient of discharge of iron pentacarbonyl(gt). liquid Fe(CO)5 through a nozzle has many important
advantages over the present method of feeding with prior
vaporization, namely:
1. Possibility of converting the process to fully
automatic operation.
Water ~ w.zx~ ~ ~ ' ~ W a t e r
2. High accuracy of carbonyl feed regulation.
3. Prevention of clogging as a result of the use of
pressure behind the nozzle.
4. Simplification of the existing plant, resulting
from the elimination of the units comprising pressurized
measuring tanks and vaporizers, and bulky connections
between vaporizers and the thermal decomposition apparatus.
..q..a
5. Reduction of losses, due to the elimination of
!
vaporizers.
Fig. 6. Single-component head with forced cooling 6. Increase of productivity, and reduction of cost
system, for atomization of iron pentacarbonyl fed of the resultant iron powder.
into nozzle through central tube.
In 1958, A. D. Pronina and N. A. Belozerskii
developed a general method for the preparation of
homogeneous metal and alloy powders, consisting in the introduction of atomized carbonyls of various methals into
a preheated chamber [8]. At the same time, an independent study was conducted by us with the object of producing
fine carbonyl iron powder for electronic purposes. The experiments were performed in a large-size installation for
the thermal decomposition of atomized liqnid iron pentacarbonyt, constructed in accordance with a process flow
sheet developed earlier.
The process is illustrated by the diagram of the installation, shown in Fig. 1. In the tank, which is filled with
Fe(CO)5, a constant inert gas (nitrogen) pressure is maintained by means of an accurate reducing valve. The carbonyl

234
 mS

Fig. 7. Two-component head with forced cooling

system, for a t o m i z a t i o n of iron pentacarbonyl fed Fig. 8. Structure of particles of iron powder
into n o z z l e through central tube. The second c o m - prepared by t h e r m a l decomposition of a t o m i z e d
ponent ( a m m o n i a gas) is fed from the side. Central iron pentacarbonyl. Distinct "onion ~ structure
tube has provision for axial adjustment. visible.

passes through the siphon trap of the tank and proceeds to coarse and fine filters, in which its m e c h a n i c a l contaminants
are extracted, after which it enters the nozzle head. The latter is mounted on the top cover of the thermal decomposi-
tion apparatus, which is resistance heated in three sections with independent current regulation.

The c y l i n d r i c a l portion of the apparatus is 4 m high and 0.5 m in d i a m e t e r . The apparatus is thoroughtyinsulated
with firebrick and asbestos. Apart from Fe(CO)s, gaseous a m m o n i a is fed into the nozzle in the cover of the apparatus.
This is done in order to inhibit the r e a c t i o n of free carbon formation, resulting from the decomposition of carbon
monoxide according to the equation
2C0 = C + CO2,
and with the object of i m p l a n t i n g the iron nitrides forming during the process into the inner layers of iron powder
particles. Both these measures improve the e l e c t r o m a g n e t i c properties of cores. The powder produced by thermal
decomposition is c o l l e c t e d in the tanks of the decomposition apparatus (80%) and filter (20%).

In the investigation, use was m a d e of centrifugal nozzles of screw and tangential types. The choice of these
nozzles was dictated by the fact that centrifugal nozzles secure much better a t o m i z a t i o n than those of any other
type, including the widely e m p l o y e d j e t nozzles [6].

The principle of operation of a centrifugal nozzle is that the fed liquid is set in rotary motion within the latter
and, under the influence of centrifugal forces, forms a thin film, which e x t r e m e l y rapidly disintegrates into very fine
droplets. In a tangential nozzle, this rotation is produced by the actual j e t of the liquid, which enters at right angles
to the centerline of the nozzle, but tangentially to the internal surface of the c y l i n d r i c a l nozzle body. In a screw
nozzle, a special swirler (screw) is provided. Figures 2 and 3 show cross sections of the nozzles used in this investigation,

C a l c u l a t i o n of centrifugal nozzles of both tangential and screw types is performed with the formula

o, = f,. g 2 g . ap..r,
where f is the cross sectional surface area of the iron pentacarbonyl outlet orifice, mr;/~ is the coefficient of dis-
charge, which takes into account j e t contraction and other factors; _g is a c c e l e r a t i o n due to gravity, m/sec2; & p is
the pressure drop of iron pentacarbonyl at the outlet, N/m2; Y is the specific gravity of iron pentacarbonyl, N/m 3.
At the beginning of the calculation, the required spray angle (2 a) is decided upon. Next, graphs (Figs. 4 and 5)
are used for determining the g e o m e t r i c a l nozzle characteristic (A) and the coefficient of discharge g, which is
governed by this characteristic [6, 7].

235
120
LO

TABLE 1. Selection of Technological Parameters for Iron Pentacarbonyl Decomposition Process

T~ Chem. composition, % Electromagnetic parameters

r filter apparatus fiiter apparatus

d
z 5 Mcps 50 Mcps 50 Mcps
o,m

o) K C N
c/>
Qrel. p ef. Qrel. ~ ef. Qrel. t~ef, I Qrel. /~ef.

295 280 300 0,73 0,67 1,11 0.91 2,02 2,93 0,91 1,78 2,95 0,83 1,78
0,62 0,83 0,77 2,10 3,04
~808O 295 24O 300 0,62 1,07 1,78 3,14 0,45 1,86
280 295 220 300 0,60 0,58 0,80 0,78 2,08 2,91 0,90 1,78 2,96 0,61 1,86

280 315 240 300 0,70 0,72 1,02 0,90 2,11 2,88 0,89 1,77 3,12 0,78 1,79
280 295 240 300 0,63 0,57 0,83 0,77 2,06 2.92 1,10 1,78 3.14 0,46 1,85
280 275 240 300 0,59 0,57 0,86 0,77 2,06 2,96 0,91 1,79 3,05 0167 1,82

7 270 295 240 300 0,58 0,56 0,91 0,84 2,03 2,90 0,97 1,78 2,95 0,53 1,86
8 280 295 240 300 0,63 0,60 0,83 0,80 2,06 2,96 1,10 1,78 3,10 0.48 1,85
9 290 295 240 300 0,68 0,63 0,95 0,96 2,04 3,04 1,07 1,82 3,09 0,72 1,82
10 3OO 295 240 300 0,74 0,66 1,07 1,06 2,05 2,97 0,93 1,81 2,98 0,83 1,80

11 295 300 240 100 0,60 0,42 1,33 0,79 2,00 2,98 0,77 1,82 3,02 0,61 1,84
12 295 295 23~ 200 0,71 0,60 1,10 0,82 2,14 2,96 0,96 1,80 2,98 0,79 1,79
13 290 295 230 300 0,63 0,63 0,80 0,79 2,10 2,94 1,07 t,82 3,09 0,72 1,82
14 270 295 24O 400 0,58 0,56 0,91 0,84 2,03 2,90 0,97 1,78 2,95 0,53 1,86
15 287 295 220 600 0,60 0,57 burnt out 2,06 2,87 0,99 1,76 burnt out
 TABLE 2. Particle Size Distribution of Iron Powders

(D
Decomposition oI atomized Decomposition of pentacarbonyl
pentacarbonyl, % vapors, %
from apparatus from filter from aRparatus fl'om filter
spherical] c o n g l o m sphericallconglom- spt~erical conglom- spherical conglom
"4 particles/crates particles crates particles Ierates particles crates
v$
/

0,5 25,70 --- 58,53 -- 17,64 -- 25,55

30,44 23,92 30,32 555 36.12
12,29 5~4 6,28 5-~2 15,46 12,85
6,35 5,34 2,53 1,68 7,13 4,55 3,34 5,72
2,82 3,32 0,10 1,21 2,38 3,66 0.96 3,34
1,71 2,72 -- 0,29 4,76 0 10 2,1l
0,10 1,00 3,56 0,10 1,85
2,87 0,62
- - 0,70
-- 1,48 I o-7o 0,90
0,40 0,20
0,33
79"~13,14 I 20,33 91-~I~ 87;1 17362 0,10
26,33 7972 20,87
Diaav, g i 1 2,59

It is characteristic of liquid iron pentacarbonyl that, at temperatures as low as about 100 ~ C, it is capabte of
decomposing appreciably into iron and carbon monoxide. Since the temperature of the unheated zone under the
cover is 180-220 ~ C, provision had to be made for cooling the nozzle in order to remove the heat received from the
gaseous phase. Two typesofheads (Figs. 6 and 7), provided with forced cooling systems, were constructed. The nozzles
were screwed into the lower part of these heads.

Experience gained in designing such heads [6] has shown that nozzles can operate at temperatures well above
those used in the carbonyl process. In our case, the water circulating continuously within the head removed heat
from the body of the head and the nozzle, thereby securing a nozzle "body" temperature of the order of 30-35 ~ C.

In contrast to the case of vapor decomposition, formation of carbonyl iron particle nuclei during the decompo-
sition of liquid iron pentacarbonyl apparently takes place not only in the upper zone, but also, to a large extent,
throughout the whole volume, which is constantly penetrated by a directional stream of very fine carbonyl droplets
projected under pressure. In consequence of this, the probability of generation of ascending convection currents is
greatly reduced. As already noted above, the absence of such currents establishes favorable conditions for the pro-
duction of fine particles 0.5-1.0 p in size.

In order to determine the optimum technological conditions, four series of experiments were carried out(Table 1)
at a constant iron pentacarbonyl feed rate of 6.5 dma/h, tn the first three series, suitable temperature conditions
were selected for each zone of the decomposition apparatus. For this purpose, the sought parameter was varied, while
the others remained constant. The results of these experiments demonstrated that the optimum temperatures for the
three zones are: top 240 ~ C, middIe 295 ~ C, and bottom 280 ~ C, which secure the best eIectromagnetic characteristics
in the resultant powder. As can be seen from Table 1, a temperature rise in any of these zones results as a rule in
increased carbon content of the powder. With temperatures as given above, however, the carbon content is an
optimum, resulting in high electromagnetic properties: 0.62- 0.63% C for the filter powder and 0.83%C for the pow-
der from the decomposition apparatus (the whole of the carbon is in the combined form). This is confirmed also by
the earlier investigations into the effect of carbon content on the electromagnetic parameters of magnetic powder
materials.

In the fourth series of experiments, the optimum conditions were employed while ammonia feed was varied in a
wide range, between 100 and 600 dm3/h. It was established in this way that the best electromagnetic parameters are
exhibited by the powder produced at an ammonia feed rate of 800' dm3/h. In such a case, the amount of combined
nitrogen is 0.63~ for the filter powders and 0.79~ for the powder from the decomposition apparatus.

237
CA
O0

TABLE 3. Comparison of Quality of Powders Produced by Nozzle Atomization and Currently Manufactured Soviet Powders

Grade R-4 gr. I R-10a R-10 R-20 R-50 R-100

Powder discharge Apparatus Filter Apparatus Filter Filter Filter

place

Powder insulation 4% bakelite 4% bakelite 0.2% water 0.2~ water 20% polystyrene 0.2% water
varnish varnish glass + 4% glass + 4% glass + 4%
bakelite varnish bakelite varnish bakelite varnish
Electromaguetic 5 Mcps 5 Mcps 5 Mcps 5 Mcps 5 Mcps 50 Mcps
core parameters
~rel. ~ ef. ~rel ~ef. Qrel. ~ ef. Qrel. ~ef. Qrel. /~e
/~ef. Qrel. /lef .
T echn. Spec. 1.75 2.80 1.85 2.95 1.85 2.90 2.00 2.95 0.90 1.,
1.40 1.10 1~65

Industrial powder 1.77-- 3.03 1.80 3.00 1.86- 3.0- 2.00- 3.02- 0.92 1.
1.50 After additional
1.84 3.10 1.98 3.08 .94 3.06 2.03 3.08 separation
1.12 I 1.62
Powder from nozzle 1.77- 3.04 2.0- 3.0- 1.85- 3.O4 2.04- 2.88- 0.98 1.65 No additional
process 1.84 3.10 2.05 3.03 1.90 3.10 2.10 3.04 1.i0 separation
0.97- I 1.78-
1.10 1.82

Note: Powders from the apparatus are also used for grade R-50 in industry.
 At the optimum conditions, the carbon to nitrogen ratio in all four series was close to unity. It would appear
that this ratio ensures the preparation of powder with high electromagnetic parameters. With the aid of Table 1, it
is also possible to examine the effect of different technological conditions on electromagnetic parameters, which is
of interest from the viewpoint of study of the technology of the process.

The powder produced under the selected conditions was subjected to particle size analysis. For this purpose,
powder samples were placed on microscope slides, and particles of different sizes were counted at a magnification
of 1380 diameters. The samples were prepared in such a manner that each slide held about 1000 particles. The
results of these counts are shown in Table 2.
The particle size analysis demonstrated that the mean particle size of iron powder produced by the new method
is smaller than that of powders prepared by the present vapor-phase decomposition process. 82.48% of the new pow-
der from the filter consisted wholly of particles 1.0 g in size or smaller. There was a corresponding increase in the
amount of such particles in the powder from the decomposition apparatus.
An electron microscopical study, carried out by A. A. Petrova, of the structare of powder prepared by the
author clearly revealed the typical "onion', structure of carbonyl iron powders. The investigation consisted in making
a microsection from a cylindrical core, etching it with r~itric acid for bringing out the structure relief, preparing
on this relief a two-stage (collodion-carbon), 100-200 A thick replica film reproducing the relief configuration, and,
finally, photographing the carbon replica under the electron microscope (Fig. 8).
The small particle size and the regular, spherical particle shape of the new powder, the presence of the
"onion" structure, and the optimum carbon and nitrogen contents are responsible for the electro-magnetic properties
of the new powder, whether discharged from the filter or the decomposition apparatus, being superior to those of
powders currently manufactured in the U. S. S. R. (Table 3).
In fact, the fine filter powder (20% of the whole amount), with the bulk of particles 0.5-1.0 g in size, is
superior- as regards Qrel. and g ef. values- to class "R- 50" powder, and approaches class "R- 100" powder, signifi-
cantly surpassing it in the/lef" value. This powder may be used as "R-10a" powder, and is superior to class"R-20"
powder in the Qrel. value, while approaching it in the gef. value. The coarser powder from the decompositon
apparatus (80~ of the whole amount) may be used as "R-4 grader' and "R-10" powders. In the latter case, its gef.
value is greater than required.
The above data on particle size distribution and electromagnetic properties show that the new process permits
production of fine iwn carbonyt powder with a predominant particle size of 0.5-1.0 g, whose properties satisfy
present-day electronic industry requirements. Furthermore, the simultaneously produced powder with coarser parti-
cles has properties Which are not inferior to those of the currently manufactured Soviet powder.

SUMMARY
1. A new method is proposed for the preparation of electronic iron powders by the thermal decomposition of
liquid iron pentaearbow1 atomized by means of centrifugal nozzles.
2. A technological process has been developed for the production of powders by the new method. Powder has
been produced in the form of two fractions-a fine one from the fiker (20%) and a coarser one from the decomposi-
tion apparatus (8C07o). The fine fraction consists mainly of particles 0.5-1.0 ~ in size.

3. The electromagnetic parameters of both fractions meet present-day electronic industry requirements.

LITERATURE CITED

1. V.L. Volkov, 1[. S. Tolmasskii, and A. E. Fridenberg, Izv. Akad. Nauk SSSIL Set. Fiz., 12, 1483 (1961).
2. C.E. Richards, Post Office Eng. Res. station (1952).
3. R.S. Fraiman, V. G. Syrkin, and V. L. Volkov, Khim. Prom., 7, 50 (1961).
4. L.B. Pfeil, Symposium on Powder Metallurgy, Iron and Steel Inst. (London), Spec. Rep., No. 38, 47 (1947).
5. A.D. Pronina and N. A. Belozerskii, U. S. 8. R. Author's Certificate (patent) No. 121, 935 (1958).
6. G.B. Sinyarev and M. V. Dobrovol'skii, Liquid Fuel Rocket Motors [in Russian] (Moscow, Oborongiz) (1955).
7. G.N. Abramovich, Jet Engine Gas Dynamics [in Russian] (Moscow) (1947).
8. I.S. Tolmasskii and A. E. Fridenberg, Plast. Massy, 12, 18 (1961).
9. V.G. Syrkin, Byul. Tekhn.-Ekon. Inform., 2, 9 (1968).

239